AU729314B2

AU729314B2 - Novel derivatives of carbocyclic fused naphthopyrans

Info

Publication number: AU729314B2
Application number: AU96740/98A
Authority: AU
Inventors: Jibing Lin
Original assignee: Transitions Optical Inc
Current assignee: Transitions Optical Inc
Priority date: 1997-10-16
Filing date: 1998-09-29
Publication date: 2001-02-01
Anticipated expiration: 2018-09-29
Also published as: WO1999020619A1; DE69809584D1; AU9674098A; US5783116A; EP1027346B1; DE69809584T2; EP1027346A1

Description

06-09-1999 US 009820468 o 0 -1- EPO-Munich 51 NOVEL DERIVATIVES OF CARBOCYCLIC FUSED NAPHTHOPYRAft Sep t DESCRIPTION OF THE INVENTION The present invention relates to certain novel derivatives of naphthopyran compounds. More particularly, this invention relates to novel derivatives of photochromic carbocyclic fused naphthopyran compounds and to compositions and articles containing such novel compounds. When exposed to electromagnetic radiation containing ultraviolet rays, such as the ultraviolet radiation in sunlight or the light of a mercury lamp, many photochromic compounds exhibit a reversible change in color. When the ultraviolet radiation is discontinued, such a photochromic compound will return to its.

original color or colorless state.

Various classes of photochromic compounds have been synthesized and suggested for use in applications in which a sunlight-induced reversible color change or darkening is desired. U.S. Patent 3,567,605 (Becker) describes a series of pyran derivatives, including certain benzopyrans and naphthopyrans. These compounds are described as derivatives of chromene and are reported to undergo a color change, e.g., from colorless to yellow-orange, on irradiation by ultraviolet light at temperatures below about -30 0 C. Irradiation of the compounds with visible light or upon raising the temperature to above about 0OC is reported to reverse the coloration to a colorless state.

U.S. Patent 5,066,818 describes various 3,3-diaryl- 3H-naphtho(2,1-b]pyrans as having desirable photochromic properties, high colorability and acceptable fade, for ophthalmic and other applications. Also disclosed by way of comparative example in the '818 patent are the isomeric 2,2diaryl-2H-naphtho[l,2-b]pyrans, which are reported to require unacceptably long periods of time to fade after activation.

U.S. Patent 5,565,147 describes certain 3,3'- R z substituted-3H-naphtho2, 1-b]pyrans having a substituted or Usubstituted five or six member oxygen or nitrogen-containing 'terocyclic ring fused to the g, i, or 1 side of the O 00 naphthopyran.

06-09-1999 US 009820468 S6 0 O. *0 s 0 0 *e a S: *0 O 00 o 2 U.S. Patent 3,627,690 describes photochromic 2,2di-substituted-2H-naphtho[1,2-b]pyran compositions containing minor amounts of either a base or weak-to-moderate strength acid. The addition of either an acid or base to the naphthopyran composition is reported to increase the fade rate of the colored naphthopyrans, thereby making them useful in eye protection applications such as sunglasses. It is reported therein further that the fade rate of 2H-naphtho- (1,2-b]pyrans without the aforementioned additives ranges from several hours to many days to reach complete reversion.

U.S. Patent 4,818,096 discloses purple/blue coloring photochromic benzo- or naphthopyrans having at the position alpha to the oxygen of the pyran ring a phenyl group having a nitrogen containing substituent in the ortho or para positions. U.S. Patent 5,645,767 describes novel photochromic indeno-fused 2H-naphtho[l,2-blpyran compounds, the 2,1positions of the indeno group being fused to the f side of the naphthopyran. U.S. Patent 5,458,814 discloses photochromic 2H-naphtho[1,2-b]pyran compounds having certain substituents at the number 5 and 6 carbon atoms of the naphtho portion of the naphthopyran and at the 2-position of the pyran ring.

The present invention relates to novel derivatives of carbocyclic fused substituted naphthopyran compounds," e.g., pentahydrophenanthropyrans and tetrahydrocyclopentanaphthopyrans, having certain substituents at the 2 position of the pyran ring. Photochromic compounds of the present invention include compounds that exhibit acceptable photochromic performance properties, i.e., activated intensity, coloration rate and fade rate.

DETAILED DESCRIPTION OF THE INVENTION In recent years, photochromic plastic materials, particularly plastic materials for optical applications, have been the subject of considerable attention. In particular, photochromic ophthalmic plastic lenses have been investigated because of the weight advantage they offer, vis-&-vis, glass (lenses. Moreover, photochromic transparencies for vehicles,

J

AftACtKrCn CLUCT 06-09-1999 US 009820468 s* a** 6a,. 00 00 0 0 0.

@0 3 such as cars and airplanes, have been of interest because of the potential safety features that such transparencies offer.

In accordance with the present invention, it has now been discovered that certain novel pentahydrophenanthro[9,10-b]pyrans and tetrahydrocyclopenta- [c]-naphtho[l,2-b]pyrans may be prepared. These compounds may be described as phenanthropyrans having hydrogen atoms at each of the number 5, 6, 7 or 8 carbon atoms of the phenanthro portion of the compound, and cyclopenta-[c]-naphthopyrans having hydrogen atoms at the number 5, 6 or 7 carbon atoms thereof, both having hydrogen atoms and certain other substituents at the 2 position of the respective pyran rings.

Certain substituents may also be present at the number 9, 11 or 12 ring atoms of the phenanthropyran compound and at the number 8, 9, 10 or 11 ring atoms of the cyclopenta-[c]naphthopyran compound.

The foregoing described phenanthropyran compounds and cyclopenta-[c]-naphthopyran compounds may be represented by the following graphic formulae I and respectively. In graphic formula I, the numbers 1 through 12 identify the ring atoms of the phenanthropyran and in graphic formula the numbers 1 through 11 identify the ring atoms of the cyclopenta-[c]-naphthopyran. In the definition of the subsitutents shown in graphic formulae I and like symbols have the same meaning unless stated otherwise.

7 S B

B

B' BI n (Rj)n I

I'

TR In graphic formulae I and each R 1 is selected from the group consisting of C 1

-C

6 alkyl, C 1

-C

6 alkoxy, chloro, fluoro, the unsubstituted, mono-,'di- or tri- S3 substituted aryl groups, phenyl and naphthyl, and the 06-09-1999 US 009820468 0 00.

-4unsubstituted, mono- and di-substituted heteroaromatic groups pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazolyl and fluorenyl, each of said aryl and heteroaromatic substituents being selected from the group consisting of aryl, mono(Cl-C 6 )alkoxyaryl, di (Cl-C 6 alkoxyaryl, mono(Cl-C 6 alkylaryl, di (Cl-C 6 )alkylaryl,

C

3

-C

7 cycloalkylaryl, C 3

-C

7 cycloalkyl, C 3

-C

7 cycloalkyloxy,

C

3

-C

7 cycloalkyloxy(C 1

-C

6 )alkyl, C 3

-C

7 cycloalkyloxy(Cl-C 6 )alkoxy, aryl (Cl-C 6 )alkyl, aryl (Cl-C 6 alkoxy, aryloxy, aryloxy(Cl-C 6 alkyl, aryloxy(C 1

-C

6 )alkoxy, mono- and di (C 1

-C

6 alkylaryl (C 1

-C

6 alkyl, mono- and di(Cl-C 6 )alkoxyaryl(C 1

-C

6 )alkyl, mono- and di(C 1

-C

6 )alkylaryl(Cl-C 6 )alkoxy, mono- and di (Cl-C 6 )alkoxyaryl(Cl-C 6 )alkoxy, di (Cl-C 6 )alkylamino, diarylamino, N- (Cl-C 6 alkylpiperazino, N-arylpiperazino, aziridino, indolino, piperidino, arylpiperidino, morpholino, thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrryl, Cl-C 6 alkyl, cj-c 6 fluoroalkyl, C 1

-C

6 alkoxy, and* mono(C 1

-C

6 )alkoxy(C 1

-C

4 )alkyl, and'n is the integer 0, 1, 2 or 3.

Preferably, each R, is selected from the group consisting of C 1

-C

4 alkyl, Cl-C 4 alkoxy, chioro, fluoro, phenyl, mono-substituted phenyl and di- substituted phenyl, preferably substituted in the meta and/or para positions and the unsubstituted, mono- and di-substituted heteroaromatic groups furanyl, benzofuran-2-yl, thienyl, benzothien-2-yl, dibenzofuran-2-yl and dibenzothien-2-yl, each of said phenyl and heteroaromatic substituents being selected from the group consisting of aryl, aryloxy, aryl(CI-C 3 )alkyl, di (Cl-C 3 alkylamino, N- (C 1

C

3 )alkylpiperazino, indolino, piperidino, morpholino, pyrryl, Cl-C 3 alkyl, Cl-C 3 Ps~- fluoroalkyl, Cl-C 3 alkoxy, and mono (C -C 3 alkoxy(Cl-C 3 alkyl, iSand n is the integer 0, 1 or 2. More preferably, each R, is selected from the group consisting Of C17C 3 alkyl, C 1

-C

3 alkoxy, phenyl, mono- and di-substituted phenyl and the ARAe:Klr'r-r CWL-CT 06-09-1 9 99 US 009820468 unsubstituted, mono- and di-substituted heteroaromatic groups furanyl, benzofuran-2-yl, thienyl and benzothien-2-yl, each of said phenyl and heteroaromatic substituents being selected from the group consisting of C 1

-C

3 alkyl, C 1

-C

3 alkoxy, aryl and indolino, and n is the integer 0 or 1.

-B and B'I in graphic formulae I and I, may each be selected from the group consisting of: the unsubstituted, mono-, di- and trisubstituted aryl groups, phenyl and naphthyl; (ii) the unsubstituted, mono- and di-substituted heteroaromatic groups pyridyl, furanyl, benzofuran-2 -yl, benzofiiran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazolyl. and fluorenyl, each of said aryl. and heteroaromatic s ubstituents in parts Mi and (ii) being selected from the group consisting of hydroxy, aryl, mono(C 1

-C

6 )alkoxyaryl, di (Cl-C 6 )alkoxyaryl, mono (Cl-C 6 alkylaryl, di (C 1 7C 6 )alkylaryl, bromoaryl, chioroaryl, fluoroaryl, C 3

-C

7 cycloalkylaryl,

C

3

-C

7 cycloalkyl, C 3

-C

7 cycloalkyloxy,

C

3

-C

7 cycloalkyloxy(Cl-C 6 alkyl, C 3

-C

7 cycloalkyloxy(Cl-C 6 alkoxy, aryl (Cl-C6)alkyl, aryl(Cl-C 6 alkoxy, aryloxy, aryloxy(Cl-C 6 )alkyl, aryloxy(C 1

-C

6 alkoxy, mono- and di(C 1 -C6)alkylaryl(C 1 -Cg)alkyl, mono- and di (Cl-C 6 alkoxyaryl (Cl-C 6 )alkyl, mono- and di (Cl-C 6 )alkylaryl (Cl-C 6 alkoxy, mono- and di (Cl-C 6 alkoxyaryl (Cl-C 6 alkoxy, amino, mono (C 1

-C

6 alkylamino, di (Cl-C 6 )alkylamino, diarylamino, N-

(C

1

-C

6 alkylpiperazino, N-arylpiperazino,. aziridino, indolino, piperidino, arylpiperidino,.morpholino, thiomorpholino, tetra1bydroquinolino, tetrahydroisoquinolino, pyrryl, Cl-C 6 alkyl, CI-C 6 bromoalkyl, CI-C 6 chioroalkyl, Cl-C 6 fluoroalkyl, Cl-C 6 alkoxy, mono(Cj-Cg)alkoxy(C 1

-C

4 )alkyl, acryloxy, rnethacryloxy, bromo, chioro and fluoro; (iii) the groups represen ted by the following 1 aphic formulae: 06-09-1 999 US 009820468 6 O s g e R3 R39 3 0 6 niroen E iscrosi irgnsbtte>R 3 bin whrein, Ehr maoerbo or oxyenR ad eac maydeogen or lC alsel;cted from the group e conisin of hyrgn,;- 6 ly (iv) Cj-C 6 alkyl*, C 1

-C

6 bromoalkyl, Cl-C 6 chioroalkyl, Cj-CG fluoroalkyl, Cj-C6 alkoxy(Cl-C 4 )alkyl,

C

3

-C

6 cycloalkyl, mono (Cl-C 6 alkoxy(C 3

-C

6 cycloalkyl, mono (Cl-C 6 alkyl (C 3

-C

6 cyci~oalkyl,-.bromo

(C

3

-C

6 cycloalkyl, chioro (C 3

-C

6 cycloalkyl and fluoro(C 3

-C

6 cycloalkyl; and the group represented by the'following graphic formula:

C=C

x z

'IC

wherein X in graphic formula IIC may be hydrogen or Cl-C 4 alkyl and Z in graphic formula IIC may be selected from the unsubstituted, mono-, and di-substituted members of the group consisting of naphthyl, phenyl, furanyl and thienyl, each of said group substituents in this part being Cl-C 4 alkyl, Cl-C 4 alkoxy, bromo, fluoro or chioro; or (vi) B and BI taken together form fluoren-9-.

ylidene, mono- or di-substituted fluoren-9-ylidene or form a member selected from the group consisting of saturated C-1 AfRAtrInCrM OLJCCT WO 99/20619 WO 9920619PCT/US98/20468 -7spiro-monocyclic hydrocarbon rings, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene, cyclononylidene, cyclodecylidene cycloundecyl idene and cyclododecylidene; saturated C 7

-C

1 2 spiro-bicyclic hydrocarbon rings, e.g., bicyclo[2.2.l3heptylidene, norbornylidene, 1,7,7trimethyl bicyclo[2 llheptylidene, bornylidene, bicyclo[3.2.lloctylidene, bicyclo[3.3.l1nonan-9-ylidene and bicyclo[4.3.2]undecane and saturated C 7

-C

1 2 spiro-tricyclic hydrocarbon rings, tricyclo[2.2.l.0 2 6 lheptylidene and tricyclo[3.3.l.1 ]decylidene, adamantylidene, and tricyclo[5.3.1 2,6~ dodecylidene, each of said fluoren-9ylidene substituents being selected from the group consisting Of Cl-C 4 alkyl, C 1

-C

4 alkoxy, bromo, fluoro and chioro.

Preferably, B and B' are each selected from the group consisting of: phenyl, mono- substituted phenyl and di-substituted phenyl, preferably substituted in the meta and/or para positions; (ii) the unsubstituted, mono- and disubstituted heteroaromatic groups furanyl, benzofuran-2-yl, thienyl, benzothien-2-yl, dibenzofuran-2-yl and dibenzothien- 2-yl, each of said phenyl and heteroaromatic substituents in Ci) and (ii) being selected from the group consisting of hydroxy, aryl, aryloxy,. aryl(C-C 3 )alkyl, amino, mono (Cl-C 3 alkylamino, di (Cl-C 3 alkylamino, N- (Cl-C 3 alkylpiperazino, indolino, piperidino, morpholino, pyrryl, Cl-C 3 alkyl, Cl-C 3 chloroalkyl, cI-c 3 fluoroalkyl, Cl-C 3 alkoxy, mono (Cl-C 3 alkoxy C 1

-C

3 alkyl, fluoro and chloro; (iii) the groups represented by the graphic formulae IIA and IIB, wherein E is carbon and D is oxygen, R 2 is Cl-C 3 alkyl or C 1

-C

3 alkoxy, R 3 and R 4 are each hydrogen or lC alkyl; and p is the integer 0 or 1; (iv) C 1

-C

4 alkyl; and (v) the group represented by the graphic formula IIC wherein X is WO 99/20619 PCT/US98/20468 8 hydrogen or methyl and Z is phenyl or mono-substituted phenyl, said phenyl substituent being selected from the group consisting of C 1

-C

3 alkyl, C 1

-C

3 alkoxy and fluoro; or (vi) B and B' taken together form fluoren-9-ylidene, mono-substituted fluoren-9-ylidene or a member selected from the group consisting of saturated C 3

-C

8 spiro-monocyclic hydrocarbon rings, saturated C 7

-C

10 spiro-bicyclic hydrocarbon rings and saturated C 7

-C

10 spiro-tricyclic hydrocarbon rings, said fluoren-9-ylidene substituent being selected from the group consisting of C 1

-C

3 alkyl, C 1

-C

3 alkoxy, fluoro and chloro.

Most preferably, B and B' are each selected from the group consisting of phenyl, mono- and di-substituted phenyl; (ii) the unsubstituted, mono- and di-substituted heteroaromatic groups furanyl, benzofuran-2-yl, thienyl and benzothien-2-yl, each of said phenyl and heteroaromatic substituents in and (ii) being selected from the group consisting of hydroxy, C 1

-C

3 alkyl, C 1

-C

3 alkoxy, aryl, indolino, fluoro and chloro; and (iii) the group represented by graphic formula IIA, wherein E is carbon and D is oxygen,

R

2 is C 1

-C

3 alkyl or C 1

-C

3 alkoxy, R 3 and R 4 are each hydrogen or CI-C 3 alkyl, and p is the integer 0 or 1; or (iv) B and B' taken together form fluoren-9-ylidene, adamantylidene, bornylidene, norbornylidene or bicyclo[3.3.1]nonan-9-ylidene.

Compounds represented by graphic formula I may be prepared by the following Reactions A through E. Compounds represented by graphic formula V or VA are either purchased or prepared by Friedel-Crafts methods shown in Reaction A using an appropriately substituted or unsubstituted benzoyl chloride of graphic formula IV with a commercially available substituted or unsubstituted benzene compound of graphic formula III. See the publication Friedel-Crafts and Related Reactions, George A. Olah, Interscience Publishers, 1964, Vol.

WO 99/20619 PCT/US98/20468 9 3, Chapter XXXI (Aromatic Ketone Synthesis), and "Regioselective Friedel-Crafts Acylation of 1,2,3,4- Tetrahydroquinoline and Related Nitrogen Heterocycles: Effect on NH Protective Groups and Ring Size" by Ishihara, Yugi et al, J. Chem. Soc., Perkin Trans. 1, pages 3401 to 3406, 1992.

In Reaction A, the compounds represented by graphic formulae III and IV are dissolved in a solvent, such as carbon disulfide or methylene chloride, and reacted in the presence of a Lewis acid, such as aluminum chloride or tin tetrachloride, to form the corresponding substituted benzophenone represented by graphic formula V (or VA in Reaction R and R' represent possible substituents, as described hereinbefore with respect to graphic formula I (or Reaction A R COC1 0 O O ^A Cl 3 2 O

CH

2 C1 2

R

III IV V In Reaction B, the substituted or unsubstituted ketone represented by graphic formula VA, in which B and B' may represent groups other than substituted or unsubstituted phenyl, as shown in graphic formula V, is reacted with sodium acetylide in a suitable solvent, such as anhydrous tetrahydrofuran (THF), to form the corresponding propargyl alcohol represented by graphic formula VI. Propargyl alcohols having B or B' groups other than substituted and unsubstituted phenyl may be prepared from commercially available ketones or ketones prepared via reaction of an acyl halide with a substituted or unsubstituted benzene, naphthalene or WO 99/20619 PCT/US98/20468 10 heteroaromatic compound. Propargyl alcohols having a B or B' group represented by graphic formula IIC may be prepared by the methods described in U.S. Patent 5,274,132, column 2, lines 40 to 68.

Reaction B

O

B B B B' HC CNa THF HO C= CH c B \B' In Reaction C, ethyl-2-cyclohexanonacetate (represented by graphic formula VII), which may be purchased, is reacted with a base such as potassium hydroxide in the presence of water and ethanol to form 2-cyclohexanonacetic acid as represented by graphic formula VIII.

Reaction C

KOH

EtOH Water VII VIII In Reaction D, compound VIII is reacted with two equivalents of the phenyl magnesium bromide represented by graphic formula IX (or other phenyl Grignard reagent) in a suitable solvent such as tetrahydrofuran (THF) to form the corresponding 2-(2-phenyl-2-hydroxycyclohexyl) acetic acid represented by graphic formula X. The compound represented by WO 99/20619 PCT/US98/20468 11 graphic formula X is cyclized with polyphosphoric to form the corresponding naphthol represented by formula XI.

acid (PPA) graphic Reaction D 2 Mg B r

TH

1 (R (R) (Rj)n VIII X XI In Reaction E the propargyl alcohol represented by graphic formula VI is coupled with the naphthol represented by graphic formula XI in the presence of an acid such as ptoluene sulfonic acid (PTSA) in a suitable solvent such as chloroform to form compounds represented by graphic formula I.

Reaction E HO C

C

C H CHC13 B B' Compounds represented by graphic formula I' may be prepared by Reactions A and B and the following described Reactions F through H. In Reaction F, methyl-2cyclopentanonacetate (represented by graphic formula VII'), which may be produced by the method described by M. Gingras, WO 99/20619 PCT/US98/20468 12 Tetrahedron Letter, Vol. 32, No. 50, pages 7381-7384 (1991), is reacted with a base such as potassium hydroxide in the presence of water and ethanol to form 2-cyclopentanonacetic acid as represented by graphic formula VIII'.

Reaction F 0 0 KHOH

KOH

EtOH O 0 Water VII' VIII' In Reaction G, Compound VIII' is reacted with two equivalents of the phenyl Grignard reagent represented by graphic formula IX in a suitable solvent such as tetrahydrofuran (THF) to form the corresponding 2-(2-phenyl-2hydroxycyclopentyl)acetic acid represented by graphic formula The compound represented by graphic formula X' is cyclized with polyphosphoric acid (PPA) to form the corresponding naphthol represented by graphic formula XI'.

Reaction G 2 -MgBr -s THF OH OH (Ri) n (Ri) n PPA [.7 VIII IX X' (R1)n XI, In Reaction H, the propargyl alcohol represented by graphic formula VI is coupled with the naphthol represented by graphic formula XI' in the presence of an acid such as ptoluene sulfonic acid (PTSA) in a suitable solvent such as chloroform to form compounds represented by graphic formula I' WO 99/20619 PCT/US98/20468 13 Reaction H SHO C CH OH C H B CHC1 3 Bo B B' n (Ri)n XI' VI Compounds represented by graphic formulae I and I' may be used in those applications in which organic photochromic substances may be employed, such as optical lenses, vision correcting ophthalmic lenses and plano lenses, face shields, goggles, visors, camera lenses, windows, automotive windshields, aircraft and automotive transparencies, T-roofs, sidelights and backlights, plastic films and sheets, textiles and coatings, coating compositions such as paints, and verification marks on security documents, documents such as banknotes, passports and drivers' licenses for which authentication or verification of authenticity may be desired. The tetrahydrophenanthropyrans represented by graphic formula I exhibit activated colors ranging from yellow to red.

Examples of contemplated phenanthropyran compounds and cyclopenta-[c]-naphthopyran compounds within the scope of the invention include the following: 2,2-diphenyl-2,5,6,7,8-pentahydrophenanthro[9,10b]pyran; 2,2-bis(4-methoxyphenyl)-2,5,6,7,8pentahydrophenanthro[9,10-b]pyran; WO 99/20619 PCT/US98/20468 14 2,2-diphenyl-2,5,6,7-tetrahydrocyclopenta-[c]naphtho[1,2-b]pyran; and 2,2-bis(4-methoxyphenyl)-2,5,6,7tetrahydrocyclopenta-[c-naphtho[1,2-b]pyran.

It is contemplated that the organic photochromic phenanthropyrans and cyclopenta-[c]-naphthopyrans of the present invention may be used alone, in combination with other phenanthropyrans and cyclopenta-[c]-naphthopyrans of the present invention, or in combination with one or more other appropriate complementary organic photochromic materials, organic photochromic compounds having at least one activated absorption maxima within the range of between about 400 and 700 nanometers (or substances containing same), which color when activated to an appropriate hue. The photochromic compounds of the present invention may be incorporated, e.g., dissolved or dispersed, in or associated with a polymeric organic host material used to prepare photochromic articles and.

Other than where otherwise indicated, all numbers expressing wavelengths, quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term "about".

Examples of complementary organic photochromic compounds include but are not limited to, other phenanthropyrans, other naphthopyrans, chromenes and oxazines, benzopyran compounds having substituents at the 2-position of the pyran ring including a dibenzo-fused 5 member heterocyclic compound and a substituted or unsubstituted heterocyclic ring, such as a benzothieno or benzofurano ring fused to the benzene portion of the benzopyrans, spiro(benzindoline)naphthopyrans, spiro(indoline)benzopyrans, spiro(indoline)naphthopyrans, spiro(indoline)quinopyrans, spiro(indoline)pyrans, WCV.AON:EPA-MUENCHEN 05 ;29-12-99 174:08 :CCITT ECM- +49 89 2:3994-4-5It 4 spiro (ind~line) napthoxazines, spiro (indol ins) pyridobenzoxazines, spiro (benzindoline) pyridobenzokxazines, Spiro (benzindoline) naphthoxazines, spiro(indoline)benzoxazines, and mixtures of such photochromic com~pounds. Many of such photochromic compounds are described in the open literature, Patents 3,562,172; 3,567,605; 3,578,602; 4,215,010; 4,3.42,668; 4,816,584; 4,818,096; 4,826,917; 4,880,667; 4,931,219; 5,066,818; 5,238,931, 5,274,132; 5,184,077; 5,405,958; 5,429,7741 5,458,814; 5,466,398; 5,514,82.; 5,552, 090; 5,552,091; 5,565,146; 5,573,7121 5,578,252; 5,645,767 and Japanese Patent Publication 62/195383. Spiro(indoline)pyrans are also described in the text, Technigues in Chemistry Volumne III, PhotochromismO Chapter 3, Glenn H. Brown, Editor, John Wiley and Sons, Inc., New York, 1971.

Other complementary photochromic substances concemplated are photochromic metal-dithizonates, e.g. mercury dithizonates which are described in, for example, U.S. Patent 3,361,706; and fulgides and fulgimides, the 3-furyl anid 3-thienyl fulgides and fulgimides which are described in U.S.

Patent 4,931,220 at column 20, line S through column 21, line 38.

The photochromic'articles of the present invention may cont~ain one photochromic compound or a mixture of .photochromic compounds, as desired.

Each of the photochromic substances described herein may be used in amounts (or in a ratio) such that an organic hoBt material to which the photochromic compounds or mixture of compounds is applied or in which they are 0 L

LL

PA

WO 99/20619 PCT/US98/20468 16 incorporated exhibits a desired resultant color, a substantially neutral color when activated with unfiltered sunlight, as near a neutral color as possible given the colors of the activated photochromic compounds. Neutral gray and neutral brown colors are preferred.

A neutral gray color exhibits a spectrum that has relatively equal absorption in the visible range between 400 and 700 nanometers. A neutral brown color exhibits a spectrum in which the absorption in the 400-550 nanometer range is moderately larger than in the 550-700 nanometer range. An alternative way of describing color is in terms of its chromaticity coordinates, which describe the qualities of a color in addition to its luminance factor, its chromaticity. In the CIE system, the chromaticity coordinates are obtained by taking the ratios of the tristimulus values to their sum, and Color as described in the CIE system can be plotted on a chromaticity diagram, usually a plot of the chromaticity coordinates x and y. See pages 47-52 of Principles of Color Technology, by F. W. Billmeyer, Jr., and Max Saltzman, Second Edition, John Wiley and Sons, N.Y. (1981). As used herein, a near neutral color is one in which the chromaticity coordinate values of and for the color are within the following ranges illuminant): x 0.260 to 0.400, y 0.280 to 0.400 following activation to 40 percent luminous transmission by exposure to solar radiation (Air Mass 1 or 2).

The amount of photochromic substance or composition containing same applied to or incorporated into a host material is not critical provided that a sufficient amount is used to produce a photochromic effect discernible to the naked eye upon activation. Generally such amount can be described as a photochromic amount. The particular amount used depends WO 99/20619 PCT/US98/20468 17 often upon the intensity of color desired upon irradiation thereof and upon the method used to incorporate or apply the photochromic substances. Typically, the more photochromic substance applied or incorporated, the greater is the color intensity up to a certain limit.

The relative amounts of the aforesaid photochromic compounds used will vary and depend in part upon the relative intensities of the color of the activated species of such compounds, and the ultimate color desired. Generally, the amount of total photochromic substance incorporated into or applied to a photochromic optical host material may range from 0.05 to 1.0, from 0.1 to 0.45, milligrams per square centimeter of surface to which the photochromic substance(s) is incorporated or applied.

The photochromic substances of the present invention may be applied to, associated with or incorporated into a host material such as a polymeric organic host material by various methods described in the art. Such methods include dissolving or dispersing the photochromic substance within the host material, casting it in place by adding the photochromic substance to the monomeric host material prior to polymerization; imbibition of the photochromic substance into the host material by immersion of the host material in a hot solution of the photochromic substance or by thermal transfer; providing the photochromic substance as a separate layer between adjacent layers of the host material, as a part of a polymeric film; and applying the photochromic substance as part of a coating or film placed on the surface of the host material. The term "imbibition" or "imbibe" is intended to mean and include permeation of the photochromic substance alone into the host material, solvent assisted transfer of the WO 99/20619 PCT/US98/20468 18 photochromic substance into a porous polymer, vapor phase transfer, and other such transfer mechanisms.

Compatible (chemically and color-wise) tints, i.e., dyes, may be applied to the host material to achieve a more aesthetic result, for medical reasons, or for reasons of fashion. The particular dye selected will vary and depend on the aforesaid need and result to be achieved. In one embodiment, the dye may be selected to complement the color resulting from the activated photochromic substances, to achieve a more neutral color or absorb a particular wavelength of incident light. In another embodiment, the dye may be selected to provide a desired hue to the host matrix when the photochromic substances is in an unactivated state.

The host material will usually be transparent, but may be translucent or even opaque. The host material need only be transparent to that portion of the electromagnetic spectrum, which activates the photochromic substance, i.e., that wavelength of ultraviolet (UV) light that produces the open form of the substance and that portion of the visible spectrum that includes the absorption maximum wavelength of the substance in its UV activated form, the open form.

Preferably, the host color should not be such that it masks the color of the activated form of the photochromic substance, so the change in color is readily apparent to the observer. More preferably, the host material article is a solid transparent or optically clear material, materials suitable for optical applications, such as plano and ophthalmic lenses, windows, automotive transparencies, e.g., windshields, aircraft transparencies, plastic sheeting, polymeric films, etc.

The photochromic compounds of the present invention may be present in an organic solvent or an organic polymeric WO 99/20619 PCT/US98/20468 19 host. The organic solvent may be selected from the group consisting of benzene, toluene, methyl ethyl ketone, acetone, ethanol, tetrahydrofurfuryl alcohol, N-methyl pyrrolidinone, 2-methoxyethyl ether, xylene, cyclohexane, 3-methyl cyclohexanone, ethyl acetate, tetrahydrofuran, methanol, methyl propinate, ethylene glycol and mixtures thereof.

Preferably, the organic solvent is selected from the group consisting of acetone, ethanol, tetrahydrofurfuryl alcohol, 2methoxyethyl ether, 3-methyl cyclohexanone, N-methyl pyrrolidinone and mixtures thereof.

Preferably, the organic polymeric host material is a solid transparent or optically clear material, e.g., materials suitable for optical applications, such as plano and ophthalmic lenses, windows, automotive transparencies, e.g., windshields, aircraft transparencies, plastic sheeting, polymeric films, etc.

Examples of polymeric organic host materials are polymers prepared from individual monomers or mixtures of monomers selected from the following groups: diacrylate or dimethacrylate compounds represented by graphic formula XII:

R

CH2 CCO m--OCC

CH

2 II II O O

XII

wherein R 5 and Rg may be the same or different and are hydrogen or methyl, A is methylene (CH 2 and m is an integer of from 1 to WO 99/20619 PCT/US98/20468 20 diacrylate or dimethacrylate compounds represented by graphic formula XIII:

R

5

R

6

CH

2 CC q- OCC CH 2 0 O

XIII

wherein D is CH 2

CR

6

R

7

R

7 is hydrogen or methylene and q is an integer of from 1 to 50; and an acrylate or a methacrylate compound having an epoxy group represented by graphic formula XIV:

R

8 CH CCO- CH CH-CH 0 O

XIV

wherein R 8 is hydrogen or methyl.

In graphic formulae XII, XIII and XIV, like letters used with respect to the definitions of different substituents have the same meaning.

Examples of diacrylate or dimethacrylate compounds represented by graphic formulae XII and XIII include diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, etc., butanediol dimethacrylate and poly(oxyalkylene dimethacrylates), polyethylene glycol (600) dimethacrylate. Examples of acrylate or methacrylate compounds represented by graphic formula XIV include glycidyl acrylate and glycidyl methacrylate.

WO 99/20619 PCT/US98/20468 -21 Further examples of polymeric organic host materials which may be used with the photochromic compounds described herein include: polymers, homopolymers and copolymers, of the monomers and mixtures of monomers represented by graphic formulae XII, XIII and XIV, bis(allyl carbonate) monomers, diisopropenyl benzene monomers, ethoxylated bisphenol A dimethacrylate monomers, ethylene glycol bismethacrylate monomers, poly(ethylene glycol) bismethacrylate monomers, ethoxylated phenol bismethacrylate monomers, alkoxylated polyhydric alcohol polyacrylate monomers, such as ethoxylated trimethylol propane triacrylate monomers, urethane acrylate monomers, such as those described in U.S. Patent 5,373,033, and vinylbenzene monomers, such as those described in U.S. Patent 5,475,074 and styrene; polymers, homopolymers and copolymers, of polyfunctional, mono-, di- or multi-functional, acrylate and/or methacrylate monomers, poly(C 1

-C

12 alkyl methacrylates), such as poly(methyl methacrylate), poly(alkoxylated phenol methacrylates), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), polyurethanes, thermoplastic polycarbonates, polyesters, poly(ethylene terephthalate), polystyrene, poly(alpha methylstyrene), copoly(styrene-methyl methacrylate), copoly(styrene-acrylonitrile), polyvinylbutyral and polymers, homopolymers and copolymers, of diallylidene pentaerythritol, particularly copolymers with polyol (allyl carbonate) monomers, diethylene glycol bis(allyl carbonate), and acrylate monomers, ethyl acrylate, butyl acrylate.

WO 99/20619 PCT/US98/20468 22 Transparent copolymers and blends of transparent polymers are also suitable as host materials. Preferably, the host material is an optically clear polymerized organic material prepared from a thermoplastic polycarbonate resin, such as the carbonate-linked resin derived from bisphenol A and phosgene, which is sold under the trademark, LEXAN; a polyester, such as the material sold under the trademark, MYLAR; a poly(methyl methacrylate), such as the material sold under the trademark, PLEXIGLAS; polymerizates of a polyol(allyl carbonate) monomer, especially diethylene glycol bis(allyl carbonate), which monomer is sold under the trademark CR-39, and polymerizates of copolymers of a polyol (allyl carbonate), diethylene glycol bis(allyl carbonate), with other copolymerizable monomeric materials, such as copolymers with vinyl acetate, copolymers of from 80-90 percent diethylene glycol bis(allyl carbonate) and 10-20 percent vinyl acetate, particularly 80-85 percent of the bis(allyl carbonate) and 15-20 percent vinyl acetate, and copolymers with a polyurethane having terminal diacrylate functionality, as described in U.S. patents 4,360,653 and 4,994,208; and copolymers with aliphatic urethanes, the terminal portion of which contain allyl or acrylyl functional groups, as described in U.S. Patent 5,200,483; poly(vinyl acetate), polyvinylbutyral, polyurethane, polymers of members of the group consisting of diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, ethoxylated bisphenol A dimethacrylate monomers, ethylene glycol bismethacrylate monomers, poly(ethylene glycol, bismethacrylate monomers, ethoxylated phenol bismethacrylate monomers and ethoxylated trimethylol propane triacrylate monomers; cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, polystyrene and RCV. VON -EPA-MIIjFNCIIE.N 05 ".29-12-99 ;17:08 CCITT ECM-# +4.9 89 2:3994465;# !J S. L D. 1 3 3 a VU.A1 LI U 411 InILIL L1v. J/U -23copolym~ers of styrene with methyl methacrylate, vinyl acetate ad acrylonitrile.

More particularly contemplated is use of the photochromic phananthropyrans and/or naphthopyrans of the 3 present invention with optical organic resin monomers used to produce optically clear polymerizates, materials suitable for optical applications, such as for example plane and ophthaltuic lenses, windows, and automotive transparencies.

such optically clear polymerizatea may have a refractive index that may range from about 1.48 to about 1.75, from about 1.495- to about 1.66. specifically contemplated are optioal res ins sold by PPG Industries, Inc. under the CR- designation, CR-307 and CR-407.

The present invention is more particularly 1S described in the following examples which are intended as illustrative only.

EXAM4PLE 1 Ethyl-2-cyclohexanonacetate (18.4 grams) and potassium hydroxide (16.8 grams) were added to a reaction flask containing ethanol (100 milliliters and water (100 WL. The resulting mixture was heated to and maintained at the ref lux temperature and stirred for two hours. After cooling to room temperature, the reaction mixture was acidified and extracted three times with ether. The ether extracts-were combined, washed with water and dried over anhydrous sodium sulf ate. The solvent, echer, was removed on A rotary evaporator. The recovered product (14.5 grams) was a viscous oil. A nuclear magnetic resonance (NMR) spectrum WO 99/20619 PCT/US98/20468 24 showed the product to have a structure consistent with 2cyclohexanoneacetic acid.

Step 2 The 2-cyclohexanoneacetic acid of step 1 (14.5 grams) was added to a reaction flask containing tetrahydrofuran (60 mL). Phenyl magnesium bromide (150 mL, molar in tetrahydrofuran) was slowly added to the stirred reaction mixture. The reaction mixture was stirred for one hour and then poured into a beaker containing a mixture of ice, hydrochloric acid and ether. The resulting ether layer was recovered, washed twice with water and dried over anhydrous sodium sulfate. The solvent, ether, was removed on a rotary evaporator yielding 20.9 grams of product. An NMR spectrum showed the product to have a structure consistent with 2-(2-phenyl-2-hydroxycyclohexyl)acetic acid.

Step 3 The 2-(2-phenyl-2-hydroxycyclohexyl)acetic acid of Step 2 (20.9 grams) was mixed with polyphosphoric acid (100 grams) in a 250 mL round bottom flask and maintained at a temperature of 1000C for two hours. The reaction mixture was poured into a beaker containing ice, and the resulting mixture was extracted three times with ether. The ether extracts were combined, washed twice with water and dried over anhydrous sodium sulfate. The solvent, ether, was removed on a rotary evaporator. The product was purified on a silica gel column yielding 9.4 grams of a viscous oil which slowly crystallized.

An NMR spectrum showed the product to have a structure consistent with 1,2,3,4-tetrahydrophenanthro-9-ol.

WO 99/20619 PCT/US98/20468 25 Step 4 The 1,2,3,4-tetrahydrophenanthro-9-ol of Step 3 (7.2 grams) was mixed with l,l-bis(4-methoxyphenyl)propargyl alcohol (11.3 grams) and p-toluene sulfonic acid (PTSA) (0.3 gram) in chloroform (100 mL) in a 500 mL round bottom flask.

The mixture was refluxed for six hours. After cooling to room temperature, the reaction mixture was washed twice with water and dried over sodium sulfate. The solvent, chloroform, was removed on a rotary evaporator. The product was purified on a silica gel column to yield 1.0 gram of a foamy product. An NMR spectrum showed the product to have a structure consistent with 2,2-bis(4-methoxyphenyl)-2,5,6,7,8pentahydrophenanthro[9,10-b]pyran.

EXAMPLE 2 PART A Testing was done with the photochromic compound described in Example 1 in the following manner. A quantity of photochromic compound calculated to yield a 1.5 x 10 3 molal solution was added to a flask containing 50 grams of a monomer blend of 4 parts ethoxylated bisphenol A dimethacrylate (BPA 2EO DMA), 1 part poly(ethylene glycol) 600 dimethacrylate, and 0.033 weight percent 2,2'-azobis(2-methyl propionitrile) (AIBN). The photochromic compound was dissolved into the monomer blend by stirring and gentle heating. After a clear solution was obtained, it was poured into a flat sheet mold having the interior dimensions of 2.2 mm x 6 inches (15.24 cm) x 6 inches (15.24 cm). The mold was sealed and placed in a horizontal air flow, programmable oven programmed to increase the temperature from 40 0 C to 95 0 C over a 5 hour interval, hold the temperature at 95 0 C for 3 hours, lower it to 60 0 C over a 2 hour interval and then hold at 60 0 C for 16 hours. After the' WO 99/20619 PCT/US98/20468 26 mold was opened, the polymer sheet was cut using a diamond blade saw into 2 inch (5.1 centimeters) test squares.

Part B The photochromic test squares prepared in Part A were tested for photochromic response on an optical bench.

Prior to testing on the optical bench, the phctochromic test squares were exposed to 365 nanometer ultraviolet light for about 15 minutes to activate the photochromic compounds and then placed in a 76°C oven for about 15 minutes to bleach or inactivate the photochromic compounds. The test squares were then cooled to room temperature, exposed to fluorescent room lighting for at least 2 hours and then kept covered for at least 2 hours prior to testing on an optical bench maintained at 72-F The bench was fitted with a 150 watt Xenon arc lamp, a remote controlled shutter, a copper sulfate bath acting as a heat sink for the arc lamp, a Schott WG-320 nm cut-off filter which removes short wavelength radiation; neutral density filter(s) and a sample holder in which the square to be tested was inserted. The power output of the optical bench, the dosage of light that the sample lens would be exposed to, was calibrated with a photochromic test square used as a reference standard. This resulted in a power output ranging from 0.15 to 0.20 milliWatts per square centimeter (mW/cm 2 Measurement of the power output was made using a GRASEBY Optronics Model S-371 portable photometer (Serial #21536) with a UV-A detector (Serial #22411) or comparable equipment. The UV-A detector was placed into the sample holder and the light output was measured. Adjustments to the power output were made by increasing or decreasing the lamp wattage or by adding or removing neutral density filters in the light path.

WO 99/20619 PCT/US98/20468 27 A monitoring, collimated beam of light from a tungsten lamp was passed through the square at a small angle (approximately 300) normal to the square. After passing through the square, the light from the tungsten lamp was directed to a detector through Spectral Energy Corp. GM-200 monochromator set at the previously determined visible lambda max of the photochromic compound being measured. The output signals from the detector were processed by a radiometer.

Change in optical density (AOD) was determined by inserting a test square in the bleached state into the sample holder, adjusting the transmittance scale to 100%, opening the shutter from the Xenon lamp to provide ultraviolet radiation to change the test square from the bleached state to an activated darkened) state, measuring the transmittance in the activated state, and calculating the change in optical density according to the formula: AOD=log(100/%Ta), where %Ta is the percent transmittance in the activated state and the logarithm is to the base The optical properties of the photochromic compound in the test squares are reported in Table 1. The A OD/Min, which represents the sensitivity of the photochromic compound's response to UV light, was measured over the first five seconds of UV exposure, then expressed on a per minute basis. The saturation optical density (A OD@ Sat) was taken under identical conditions as the A OD/Min, except UV exposure was continued for 15 minutes. The lambda max (Vis) is the wavelength in nanometers (nm) in the visible spectrum at which the maximum absorption of the activated (colored) form of the photochromic compound in a test square occurs.

The lambda max (Vis) wavelength was determined by testing the photochromic test square polymerizates of Part A in a Varian Cary 3 UV-Visible spectrophotometer. The lambda max (UV) WO 99/20619 PCT/US98/20468 28 is the wavelength in nanometers in the ultraviolet range closest to the visible spectrum at which the absorption of the photochromic compound occurs. This absorption was also determined with the same spectrophotometer. The Bleach Rate (T 1/2) is the time interval in seconds for the absorbance of the activated form of the photochromic compound in the test squares to reach one half the highest absorbance at room temperature (72 0 F) after removal of the source of activating light.

TABLE 1 max (VIS) 504 nm max (UV) 358 nm AOD/MIN Sensitivity 0.04 AOD@ Saturation 0.21 Bleach Rate (T 1/2) 229 seconds The present invention has been described with reference to specific details of particular embodiments thereof. It is not intended that such details be regarded as limitations upon the scope of the invention except insofar as to the extent that they are included in the accompanying claims.

Claims

06-0-199 B **US 009820468 Sep 4 *.999 claim:* 0 O @0 @o 0 copon rereene by thee B Br B0 e m 0 __0 following grpicfrmle (Rj) n (Rj) n wherein, each R, is selected from the group consisting Of Cl-C 6 alkyl, Cl-C 6 alkoxy, chioro, fluoro, the unsubstituted, mono-, di- and tri-substituted aryl groups selected from phenyl and naphthyl, and the unsubstituted, mono- and di-substituted heteroaromatic groups selected from pyridyl, furanyl, benzofuran-2-yl, henzofuran-3 -yl, thienyl, benzothien- 2-yl, benzothien-3 -yl, dibenzofuranyl, dibenzothienyl, carbazolyl and fluorenyl, each of said aryl and heteroaromatic substituents being selected from the group 1S consisting of the aryl groups selected from phenyl and naphthyl, mono (Cl-C 6 alkoxyaryl, di (Cl-C 6 alkoxyaryl, mono (Cl-C 6 alkylaryl, di (Cl-C 6 alkylaryl, C 3 -C 7 cycloalkylaryl, C 3 -C 7 cycloalkyl, C 3 -C 7 cycloalkyloxy, C 3 -C 7 cycloalkyloxy(Cl-C 6 alkyl, C 3 -C 7 cycloalkyloxy(C 1 -C)alkoxy, aryl(Cl-C 6 )alkyl, aryl(Cl-C 6 )alkoxy, aryloxy, aryloxy(C 1 -C 6 alkyl, aryloxy(Cl-C 6 alkoxy, mono- and di (Cj-C 6 )alkylaryl (Cj-C 6 )alkyl, mono- and' di (Cj-C 6 -)alkoxyaryl (Cl-C 6 alkyl, mono- and di (C 1 -C 6 )alkylaryl (CI-C 6 )alkoxy, mono- and di (C 1 -C 6 )alkoxyaryl (Cl-C 6 )alkoxy, di (CI-C 6 )alkylamino, diarylamino, N- (Cl-C 6 alkylpiperazino, N-arylpiperazino, azinidino, indolino, piperidino, arylpiperidino, morpholino, $xthiomorpholino, tetrahydroqluinolino, tetrahydroisoquinolino, 06-09-1999 US 009820468 S. :g 00 So sme em g, a* Ole's pyrryl, CI-C 6 alkyl, Cl-C 6 fluoroalkyl, Cl-C 6 alkoxy, and mono(Cj-C 6 )alkoxy(C 1 -C 4 )alkyl, and n is the integer 0, 1, 2 or 3; and B and B' are each selected from the group consisting of: (i the unsubstituted, mono-, di- and tri- substituted aryl groups selected from phenyl and naphthyl; (ii) the unsubstituted, mono- and di- substituted heteroaromatic groups pyridyl, furanyl,. benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3 -yl, dibenzofuranyl, dibenzothienyl, carbazolyl and fluorenyl, each of said aryl and heteroaromatic substituents in (bi and (ii) being selected from the group consisting of hydroxy, aryl, mono(C 1 -C 6 )alkoxyaryl, di (Cl-C 6 )alkoxyaryl, mono(C 1 C 6 )alkylaryl, di (Cl-C 6 )alkylaryl, bromoaryl, chioroaryl, fluoroaryl, C 3 -C 7 cycioalkylaryl, C 3 -C 7 cycloalkyl, C3-Cy cycloalkyloxy, C 3 -C 7 cycloalkyloxy(Cl-C 6 alkyl, C 3 -C 7 cycloalkyloxy(C 1 -C 6 alkoxy, aryl(Cl-C 6 )alkyl, aryl(Cl-C 6 )alkoxy, aryloxy, aryloxy(Cl-C 6 )alkyl, aryloxy(Cl-C 6 )alkoxy, mono- and di- (Cl-C 6 )alkylaryl (Cl-C 6 )alkyl, mono- and di- (Cj-Cr 6 )alkoxyaryl(C 1 -C 6 )alkyl, mono- and di- (Cl-C 6 )alkylaryl(Cl-C 6 )alkoxy, mono- and di-. (C 1 -C 6 )alkoxyaryl (C 1 -C 6 )alkoxy, amino, mono(Cl-C 6 )alkylamino, di (Cl-C 6 )alkylamino, diarylamino, N- (C 1 -C 6 alkylpiperazino, N- arylpiperazino, aziridino, indolino, piperidino, arylpiperidino, morpholino, thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrryl, Ci-C 6 alkyl, Cl-C 6 bromoalkyl, Ci-C 6 chioroalkyl, Cl-C 6 fluoroalkyl, Cl-CO alkoxy, mono(C 1 -C 6 alkoxy(Cj-C 4 )aJcyl, acryloxy, methacryloxy, bromo, chioro and fluoro; (iii) the groups represented by the following graphic formulae: I-r-rN ell Ir-r-IT" WO 99/20619 PCT/US98/20468 31 E R 3 ER 3 D R 4 D R4 (R 2 )p (R2)p wherein E is carbon or oxygen and D is oxygen or substituted nitrogen, provided that when D is substituted nitrogen, E is carbon, said nitrogen substituents being selected from the group consisting of hydrogen, C 1 -C 6 alkyl and C 2 -C 6 acyl; each R 2 is C 1 -C 6 alkyl, C 1 -C 6 alkoxy, hydroxy, bromo, chloro or fluoro; R 3 and R 4 are each hydrogen or C 1 -C 6 alkyl; and p is the integer 0, 1 or 2; (iv) C 1 -C 6 alkyl, C 1 -C 6 bromoalkyl, Cl-C 6 chloroalkyl, C 1 -C 6 fluoroalkyl, C 1 -C 6 alkoxy(C 1 -C 4 )alkyl, C 3 -C 6 cycloalkyl, mono(C 1 -C 6 alkoxy(C 3 -Cg)cycloalkyl, mono(C 1 -C 6 )alky(C3-C-calkyl(C-Clkyl, bromo(C 3 -Cg)cycloalkyl, chloro(C 3 -C 6 )cycloalkyl and fluoro(C 3 -Cg)cyclo-alkyl; and the group represented by the following graphic formula: \C=C X \Z wherein X is hydrogen or C 1 -C 4 alkyl and Z is selected from the unsubstituted, mono-, and di-substituted members of the group consisting of naphthyl, phenyl, furanyl and thienyl, each of said group substituents being C 1 -C 4 alkyl, C 1 -C 4 alkoxy, bromo, fluoro or chloro; or (vi) B and B' taken together form fluoren-9- ylidene, mono- or di-substituted fluoren-9-ylidene or a member selected from the group consisting of saturated C 3 -C 12 spiro- monocyclic hydrocarbon rings, saturated C7-C12 spiro-bicyclic hydrocarbon rings, and saturated C 7 -C 12 spiro-tricyclic hydrocarbon rings, each of said fluoren-9-ylidene substituents WO 99/20619 PCTIUS98/20468 32 being selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, bromo, fluoro and chloro. 2. The compound of claim 1 wherein each R 1 is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, chloro, fluoro, phenyl, mono- substituted phenyl and di-substituted phenyl, and the unsubstituted, mono- and di-substituted heteroaromatic groups furanyl, benzofuran-2-yl, thienyl, benzothien-2-yl, dibenzofuran-2-yl and dibenzothien-2-yl, each of said phenyl and heteroaromatic substituents being selected from the group consisting of aryl, aryloxy, aryl(C 1 -C 3 )alkyl, di(C 1 -C 3 )alkylamino, N-(C 1 -C 3 )alkylpiperazino, indolino, piperidino, morpholino, pyrryl, C 1 -C 3 alkyl, C 1 -C 3 fluoroalkyl, C 1 -C 3 alkoxy, and mono(C 1 -C 3 )alkoxy(C 1 -C 3 )alkyl, and n is the integers 0, 1 or 2; and B and B' are each selected from the group consisting of: phenyl, mono-substituted phenyl and di- substituted phenyl; (ii) the unsubstituted, mono-substituted and di-substituted heteroaromatic groups furanyl, benzofuran-2-yl, thienyl, benzothien-2-yl, dibenzofuran-2-yl, and dibenzothien- 2-yl, each of said phenyl and heteroaromatic substituents in and (ii) being selected from the group consisting of hydroxy, aryl, aryloxy, aryl(C 1 -C 3 )alkyl, amino, mono(C 1 -C 3 )alkylamino, di(C 1 -C 3 )alkylamino, N- (Cl-C 3 )alkylpiperazino, indolino, piperidino, morpholino, pyrryl, C 1 -C 3 alkyl, C 1 -C 3 chloroalkyl, C 1 -C 3 fluoroalkyl, C 1 -C 3 alkoxy, mono(C 1 -C 3 )alkoxy(C 1 -C 3 )alkyl, fluoro and chloro; (iii) the groups represented by the following graphic formulae: WO 99/20619 PCT/US98/20468 33 E 3 3 D R4 (R2)p (R 2 )p wherein E is carbon and D is oxygen, R 2 is C 1 -C 3 alkyl or C1-C 3 alkoxy, R 3 and R 4 are each hydrogen or C 1 -C 4 alkyl; and p is the integer 0 or 1; (iv) C 1 -C 4 alkyl; and the group represented by the following graphic formula: C\=CH X Z wherein X is hydrogen or methyl and Z is phenyl or mono- substituted phenyl, said phenyl substituent being selected from the group consisting of C 1 -C 3 alkyl, C 1 -C 3 alkoxy and fluoro; or (vi) B and B' taken together form a fluoren-9- ylidene, mono-substituted fluoren-9-ylidene or a member selected from the group consisting of saturated C 3 -Cg spiro- monocyclic hydrocarbon rings, saturated C 7 -C 10 spiro-bicyclic hydrocarbon rings and saturated C 7 -C 10 spiro-tricyclic hydrocarbon rings, said fluoren-9-xylidene substituent being selected from the group consisting of C 1 -C 3 alkyl, C 1 -C 3 alkoxy, fluoro and chloro. 3. The compound of claim 2 wherein: R 1 is selected from the group consisting of C 1 -C 3 alkyl, C 1 -C 3 alkoxy, phenyl, mono- and -d-substituted phenyl and the unsubstituted, mono- and di-substituted aromatic heterocyclic groups furanyl, benzofuran-2-yl, thienyl and benzothien-2-yl, each of said phenyl and aromatic heterocyclic substituents being selected from the group 06-09-19P9 US 009820468 so of -34- consisting of C 1 -C 3 alkyl, C 1 -C 3 alkoxy, aryl and indolino, and n is the integers 0 or 1; and B and B, are each selected from the group consisting of: phenyl, mono-substituted and di- substituted' phenyl; (ii) the unsubstituted, mono-, and di- substituted heteroaromatic groups furanyl, benzofuran-2-yl, thienyl and benzothien-2-yl, each of said phenyl and heteroaromatic substituents in and (ii) being selected from the group consisting of hydroxy, C 1 -C 3 alkyl, CI-C 3 alkoxy, aryl, indolino, fluoro and chioro; and (iii) the group represented by the following graphic formula: D R 4 (R 2 p wherein E is carbon and D is oxygen, R 2 is Cl-C 3 alkyl. or CI-C 3 alkoxy, R 3 and R 4 are each hydrogen or C 1 -C 3 alkyl, and p is the integer 0 or 1; or (iv) B and B' taken together form fluoren-9- ylidene, adamantylidene, bornylidene, norbornylidene or bicyclo nonan-9-ylidene. 4. A photochromic compound of claim 1 selected from the group consisting of: 2 2 -dipheny1-2,s,6,7,,e-pentahydrophenanthro(9,10o b~pyran; 2,2-bis(4-methoxyphenyl)-2,5,67,8-. pentahydrophenanthro(9, 2,2-diphenyl-2,5, 6, 7-tetrahydrocyclopenta-Cc] D riphthoE1,2-b~pyran; and WO 99/20619 PCT/US98/20468 35 2,2-bis(4-methoxyphenyl)-2,5,6,7-tetrahydro- 2H-cyclopenta-[c]-naphtho[1,2-b]pyran. A photochromic article comprising a polymeric organic host material and a photochromic amount of the compound of claim 1. 6. The photochromic article of claim 5 wherein the polymeric organic host material is selected from the group consisting of poly(C 1 -C 12 alkyl methacrylates), poly(oxyalkylene dimethacrylates), poly(alkoxylated phenol methacrylates), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), thermoplastic polycarbonates, polyesters, polyurethanes, poly(ethylene terephthalate), polystyrene, poly(alpha methylstyrene), copoly(styrene-methylmethacrylate), copoly(styrene- acrylonitrile), polyvinylbutyral and polymers of members of the group consisting of bis(allyl carbonate) monomers, polyfunctional acrylate monomers, polyfunctional methacrylate monomers, diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, ethoxylated bisphenol A dimethacrylate monomers, ethylene glycol bismethacrylate monomers, poly(ethylene glycol) bismethacrylate monomers, ethoxylated phenol bismethacrylate monomers, alkoxylated polyhydric alcohol acrylate monomers, styrene monomers, urethane acrylate monomers, glycidyl acrylate monomers, glycidyl methacrylate monomers and diallylidene pentaerythritol monomers.
7. The photochromic article of claim 6 wherein the polymeric organic host material is a solid transparent polymer selected from the group consisting of poly(methyl methacrylate), poly(ethylene glycol bismethacrylate), WO 99/20619 PCT/US98/20468 36 poly(ethoxylated bisphenol A dimethacrylate), thermoplastic polycarbonate, poly(vinyl acetate), polyvinylbutyral, polyurethane and polymers of members of the group consisting of diethylene glycol bis(allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, ethoxylated phenol bismethacrylate monomers, diisopropenyl benzene monomers and ethoxylated trimethylol propane triacrylate monomers.
8. The photochromic article of claim 7 wherein the photochromic compound is present in an amount of from 0.05 to 1.0 milligram per square centimeter of organic host material surface to which the photochromic substance(s) is incorporated or applied.
9. The photochromic article of claim 8 wherein said transparent polymer is an optical element. The photochromic article of claim 9 wherein said optical element is a lens.
11. A photochromic article comprising a polymeric organic host material selected from the group consisting of poly(methyl methacrylate), poly(ethylene glycol bismethacrylate), poly(ethoxylated bisphenol A dimethacrylate), thermoplastic polycarbonate, poly(vinyl acetate), polyvinylbutyral, polyurethane and polymers of members of the group consisting of diethylene glycol bis(allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, ethoxylated phenol bismethacrylate monomers, diisopropenyl benzene monomers and ethoxylated trimethylol propane triacrylate monomers, and a photochromic amount of the compound of claim 3.
12. A photochromic article comprising a polymerizate of an optical organic resin monomer and a photochromic amount of the compound of claim 1. WO 99/20619 PCT/US98/20468 37
13. the refractive to about 1.75.
14. the refractive to about 1.66. The photochromic article of claim 12 wherein index of the polymerizate is from about 1.48 The photochromic article of claim 13 wherein index of the polymerizate is from about 1.495
15. A photochromic article comprising, in combination, a solid transparent polymeric organic host material, and a photochromic amount of each of at least one compound of claim 1, and at least one other organic photochromic compound having at least one activated absorption maxima within the range of between about 400 and 700 nanometers.
16. The photochromic article of claim 15 wherein the polymeric organic host material is selected from the group consisting of poly(C 1 -C 12 alkyl methacrylates), poly(oxyalkylene dimethacrylates), poly(alkoxylated phenol methacrylates), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), thermoplastic polycarbonates, polyesters, polyurethanes, poly(ethylene terephthalate), polystyrene, poly(alpha methylstyrene), copoly(styrene-methylmethacrylate), copoly(styrene- acrylonitrile), polyvinylbutyral and polymers of members of the group consisting of bis(allyl carbonate) monomers, polyfunctional acrylate monomers, polyfunctional methacrylate monomers, diethylene glycol dimethacrylate moi.-mers, ethoxylated bisphenol A dimethacrylate monomers, diisopropenyl benzene monomers, ethylene glycol bismethacrylate monomers, poly(ethylene glycol) bismethacrylate monomers, ethoxylated phenol bismethacrylate monomers, alkoxylated polyhydric WO 99/20619 PCT/US98/20468 38 alcohol acrylate monomers, styrene monomers, urethane acrylate monomers, glycidyl acrylate monomers, glycidyl methacrylate monomers and diallylidene pentaerythritol monomers.
17. The photochromic article of claim 16 wherein the polymeric organic host material is a solid transparent homopolymer or copolymer selected from the group consisting of poly(methyl methacrylate), poly(ethylene glycol bis- methacrylate), poly(ethoxylated bisphenol A dimethacrylate), thermoplastic polycarbonate, poly(vinyl acetate), polyvinylbutyral, polyurethane and polymers of members of the group consisting of diethylene glycol bis(allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, ethoxylated phenol bismethacrylate monomers, diisopropenyl benzene monomers and ethoxylated trimethylol propane triacrylate monomers.
18. The photochromic article of claim 15 wherein the organic photochromic compound is selected from the group consisting of other phenanthropyrans, other naphthopyrans, chromenes, oxazines, metal-dithizonates, fulgides and fulgimides.
19. The photochromic article of claim 18 wherein the total amount of photochromic compound present is from 0.05 to 1.0 milligram per square centimeter of organic host material surface to which the photochromic substance(s) is incorporated or applied.
20. The photochromic article of claim 18 wherein said transparent polymeric organic host material is an optical element.
21. The photochromic article of claim 20 wherein said optical element is a lens. WO 99/20619 PCT/US98/20468 39
22. A photochromic article comprising, in combination, a polymeric organic host material selected from the group consisting of poly(methyl methacrylate), poly(ethylene glycol bismethacrylate), poly(ethoxylated bisphenol A dimethacrylate), thermoplastic polycarbonate, poly(vinyl acetate), polyvinylbutyral, polyurethane and polymers of members of the group consisting of diethylene glycol bis(allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, ethoxylated phenol bismethacrylate monomers, diisopropenyl benzene monomers and ethoxylated trimethylol propane triacrylate monomers, and a photochromic amount of each of at least one compound of claim 3, and at least one other organic photochromic compound having at least one activated absorption maxima within the range of between about 400 and 700 nanometers.